CN1469900A - Compatibilization of polymer blends using isobutylene-based block copolymers - Google Patents

Compatibilization of polymer blends using isobutylene-based block copolymers Download PDF

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CN1469900A
CN1469900A CNA018174035A CN01817403A CN1469900A CN 1469900 A CN1469900 A CN 1469900A CN A018174035 A CNA018174035 A CN A018174035A CN 01817403 A CN01817403 A CN 01817403A CN 1469900 A CN1469900 A CN 1469900A
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tbs
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compatilizer
iso
butylene
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CN1264909C (en
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M・F・茨
M·F·茨
锸┠赡尔迪
H-C·王
楚
R·克里施纳默尔迪
A·H·楚
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

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Abstract

Compatibilized blends of isobutylene polymers and unsaturated diene polymers using a compatibilizer comprising a block-graft copolymer comprising a polyisobutylene segment and C4－C6Alkyl substituted styrene polymer segments, such as poly (t-butylstyrene) segments.

Description

Use blend polymer compatible of isobutylene-based block copolymers
Invention field
The present invention relates to comprise the compatible blend of high and low unsaturated elastic body.
Background
Mainly due to their property, as excellent in resistance ozone degradation and cracked performance, improved chemically-resistant etch, improved temperature stability and unique dynamic response subsequently, be interesting in rubber industry based on vulcanized rubber low or that do not have olefinic unsaturated elastic body and a blend of higher unsaturated elastic body.These blends make and produce synergy between single elastomericss, obtain the composite blend performance combination that can not reach in single elastomerics.But these desired properties only occur under following situation: produce in blend and keep phase size less than 5 microns, general 1 micron or littler elastomerics be even blend closely, and has reached gratifying interfacial adhesion level.
Lamentedly, general knownly can not overcome the unfavorable entropy of blended because the favourable entropy of blended is too little, make and mix unfavorablely, unless have specific, favourable interaction, most polymers is also incompatible each other.Diameter dimension very inhomogeneous by the blend of routine techniques production and phase is many microns.When the solubility parameter of single polymkeric substance significantly not simultaneously, this of single polymkeric substance very uncompatibility and the consequent is obvious especially to producing and keeping required uniform, the powerless of fine phase size.This is the situation in the time will hanging down unsaturated elastic body and higher unsaturated elastic body blend.
Adopt another problem of saturated-unsaturated elastic body mixture to be that even high shear mixing produces tight dispersion, mixture is separated into blend thereafter, this blend is that the diameter dimension of very uneven and single phase is many microns.These very uneven blends generally have the performance combination of non-constant, and are poorer than single polymkeric substance usually, rather than show from phase size less than 5 microns general 1 micron or the littler closely evenly desired properties combination of blend.
A kind of scheme for the incompatible polymer consistency is blend in segmented copolymer, this segmented copolymer comprise derived from the monomeric segment of blend polymer-compatible and derived from monomeric another segment of another kind of blend polymer-compatible.For example, EP691378A discloses the blend polymer that comprises polycarbonate resin and polyisobutene, and this blend is compatible by comprise a small amount of polycarbonate-polyisobutylene block copolymer in blend composition.In addition, U.S. patent No.5,741,859 disclose the segmented copolymer of polyisobutene and polydimethylsiloxane and have advised that they are used as the purposes of compatilizer.
Two, three and the star block copolymer that comprise polyisobutene and poly-(to chloro-styrene) are existed by people such as Kennedy Polym.Mater.Sci.Eng., 63, the 371-375 page or leaf is disclosed as compatilizer in 1990.
The blend polymer that comprises the mixture of isobutene polymer and Geng Gao unsaturated elastic body such as polyhutadiene or polyisoprene is potential ozone proof, chemicals-resistant, gastight and temperature-stable as mentioned above.But the multipolymer of isobutene polymer such as polyisobutene, iso-butylene and isoprene (isoprene-isobutylene rubber), iso-butylene and to the multipolymer of ring-alkylated styrenes and their halogenation variant not with higher unsaturated elastic body as polymer-compatible based on conjugated diene monomer.In the presence of specific, extensive chemical interacted not, these different polymkeric substance had the positive free energy of mixing and are that thermodynamics is inconsistent therefore, and this is because mixture heat is normally positive less with the entropy that obtains when mixing these different polymer molecules.The result is bonding and because the weak blend mechanical property of shortage attach structure form of high interfacial tension and the difference between two blends phases.The present invention relates to by the height of introducing segmented copolymer and the improvement blend of low unsaturated elastic body.
General introduction
The invention provides a kind of compatible polymers blend, comprising:
A) be selected from following isobutene polymer: polyisobutene, contain 10wt% isoprene at the most the iso-butylene random copolymers, contain 10wt% isoprene at the most the halogenated isobutylene random copolymers, contain 20wt% at the most to the iso-butylene random copolymers of ring-alkylated styrenes, contain at the most 20wt% to the halogenated isobutylene random copolymers of ring-alkylated styrenes and their mixture;
B) the unsaturated diene polymer of at least a olefinic; With
C) be used for component (a) and compatilizer (b), this compatilizer comprises that at least one repeats the polyisobutene segment and at least one comprises C 4-C 6The block graft multipolymer of the repeating segment of cyclosubstituted vinylbenzene of alkyl and cyclosubstituted αJia Jibenyixi.
Some compatilizers comprise polyisobutene and to two, three or star block copolymer of t-butyl styrene (tbS).
The present invention also provides the covulcanization elastic composition based on these blends.
The accompanying drawing summary
Fig. 1 is the figure of the tensile stress-strain-gauging of the blend polymer for preparing in an embodiment;
Fig. 2 is the figure of the dynamic hot mechanical measurement of a kind of blend polymer of preparing in an embodiment; With
Fig. 3 is the figure of another dynamic hot mechanical measurement of the another kind of blend polymer for preparing in an embodiment.
Describe in detail
Compatilizer multipolymer used according to the invention is to comprise at least one derived from C 4-C 6The vinylbenzene that alkyl replaces or the polymer segment of αJia Jibenyixi and at least one segmented copolymer derived from the polymer segment of iso-butylene.These materials can comprise S-iB-S or iB-S-iB triblock copolymer, S-iB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, (S-iB) nThe graft copolymer of segmented copolymer, poly-S and poly-iB main chain or comprise poly-S and poly-iB segmental star shape branch copolymer, wherein iB is that iso-butylene and S are C 4-C 6Vinylbenzene or αJia Jibenyixi that alkyl replaces.For purpose of the present invention, all these materials are called block-graft copolymer.
The styrenic of block graft multipolymer partly comprises mixture a kind of or vinylbenzene or αJia Jibenyixi, this vinylbenzene or αJia Jibenyixi at the ortho position, a position or contraposition be by linearity or branching C 4-C 6Alkyl replaces.Some embodiments are chosen as styrene monomer to t-butyl styrene.
The GPC number-average molecular weight of some segmented copolymers of the present invention is 10,000-500,000, other 50,000-200,000.In some embodiments, the styrene monomer segment comprises that the remainder of 10wt% multipolymer at least and polymkeric substance comprises the iso-butylene segment.Some embodiments select block-graft copolymer for comprising 10-50wt% styrenic block copolymer segmental S-iB-S or iB-S-iB triblock copolymer.Other embodiment selects to have similarly 10-30wt% styrenic block copolymer segmental multipolymer.
These block-graft copolymers are being known in the art and can using Preparation of Catalyst by active, carbocation sequential polymerization, and this catalyzer comprises halogenation tertiary alkyl, halogenation uncle aralkyl or halogenation polymerization starter and contains aluminium trimethide or the coinitiator of methyl boron compound.Be aggregated in suitable solvent known in the art such as anhydrous methylene chloride, hexane or the mixed solvent and carry out.Typical polymerization temperature is less than-30 ℃.Some embodiment selective polymerization temperature are less than-60 ℃.These polymerization processs are disclosed in U.S. patent Nos.4 more completely, in 946,899,5,506,316 and 5,451,647.
Being characterized as of blend polymer of the present invention contains at least two kinds of components: unsaturated diene polymer component of olefinic and iso-butylene component.Unsaturated diolefine component comprises elastomerics conjugated diolefine (diolefine) polymkeric substance such as polyhutadiene, natural rubber, synthetic polyisoprenes, divinyl and multipolymer, sovprene and their mixture of 40wt% vinylbenzene or vinyl cyanide at the most.It is polyhutadiene or polyisoprene that some embodiments are selected the unsaturated component of olefinic.Unsaturated polymer also can be inelastic body and can comprise that liquid is 300-10 to wax shape polyhutadiene or number-average molecular weight, 000 butadienecopolymer.
The isobutene polymer blend component comprise polyisobutene, iso-butylene and at the most the 10wt% isoprene random polymers (isoprene-isobutylene rubber), the chlorination that comprises the 0.3-3wt% halogen or brominated butyl rubber, contain 20wt% at the most and at the most 14wt% to the random isobutylene copolymers of ring-alkylated styrenes such as p-methylstyrene (PMS) with comprise the chlorination or the bromination iBPMS multipolymer of 0.1-10mol% monochloromethyl styrene group.For halogenation iBPMS, halogen exists as the benzyl halogen on the polymer molecule.IBPMS and halogenation iBPMS multipolymer more particularly are described in U.S. patent N0.5, in 162,445.
Contriver's blend generally comprises isobutene polymer and the olefinic unsaturated polymer that is respectively the every 5-95 weight part of 95-5 weight part isobutene polymer unsaturated polymer.Some contrivers' blend generally comprises isobutene polymer and the olefinic unsaturated polymer that is respectively the every 10-50 weight part of 50-10 weight part isobutene polymer unsaturated polymer.Block-graft copolymer additive can exist by 2-20wt%, is 5-15wt% although some embodiments are selected this additive, based on the blend polymer content.
Surprisingly, comprise polyisobutene and poly-(to t-butyl styrene) segmental block-graft copolymer with the compatible blend that comprises high unsaturated elastic body such as polyhutadiene or polyisoprene because block-graft copolymer does not comprise the diene polymer segment.Unpredictable is that the styrenic polymer segment is used for compatible such elastomerics diolefine.
Block-graft copolymer can comprise 10-90wt% styrenic polymer segment, or 10-50wt% styrenic polymer segment, and remainder is the polyisobutene segment.For three block block-graft copolymers, the styrenic segment can form the interior block iB-S-iB of outer block (S-iB-S).Comprising high isobutene polymer quantity, in the blend greater than 65wt%, iB-S-iB type block-graft copolymer can be used as compatilizer.Some blocks-graft copolymer embodiment comprises the GPC number-average molecular weight and is at least 5,000, some 10,000-50,000 and some 10,000-30,000 styrenic polymer segment.
Can be with blend composition sulfuration of the present invention and goods such as sidewall, tire tread, carcass, tire lining, flexible pipe, belt, engineering goods and the similar articles of shaping to be formed with usefulness.
Suitable sulfuration or cross-linking method comprise and composition are exposed to energy-rich radiation (ultraviolet, electron beam or γ) or add suitable superoxide or promoted sulfur vulcanization system in composition.
The example of suitable peroxides comprises dialkyl peroxide, ketal superoxide, aromatic alkyl superoxide, peroxidation ether and peroxyester.Some embodiments are restricted to dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxyl benzoate and similar known free-radical generating agent with superoxide.Although it is the per 100 weight part curable polymers of 1.5-6 weight part that some embodiments are selected superoxide, the quantity of superoxide is generally the 1-10 weight part.
The mixture that comprises sulphur or sulphur and sulfur containing promoter and/or resol in the present invention as the promoted sulfur vulcanization system of vulcanizing agent.Suitable promotor comprises benzothiazyl disulfide base, N-oxygen diethylidene benzothiazole-2-sulfinyl amine, 2-mercaptobenzothiazole, alkylphenol disulphide, alkyl monosulfide thiuram, meta-phenylene bismaleimide, N, N '-diaryl guanidine, dialkyl group and diaryl dithiocar-bamate and analogous material.
Suitable dialkyl dithiocarbamate comprises the dialkyl dithiocarbamate (wherein alkyl comprises 1-5 carbon atom) of zinc, bismuth, cadmium, copper, lead, selenium and tellurium, pentamethylene dithiocarbamic acid piperidines and their mixture.
Suitable diaryl dithiocar-bamate comprises the diaryl dithiocar-bamate of zinc, bismuth, cadmium, copper, lead, selenium and tellurium and their mixture.
Suitable alkyl monosulfide thiuram comprises bis-pentamethylenethiuram tetrasulfide, tetrabutylthiuram disulfide, tetraethylthiuram disulfide, single sulfuration tetra methylthiuram, tetra-benzyl thiram disulfide and their mixture.
Usually with the 0.5-8 weight part sulphur and vulcanization accelerator are joined in the composition, based on 100 weight part vulcanizable elastomers.Promoted sulfur vulcanization system is also comprising zinc oxide or coordinator sometimes, is used as the covulcanization agent in the vulcanization system as auxiliary vulcanizing agent.Zinc oxide uses with the per 100 weight part elastomericss of 0.2-7 weight part in such system usually.
Elastic composition also can comprise other additive such as incipient scorch retarding agent, lubricant, filler, softening agent, tackifier, tinting material, whipping agent and oxidation inhibitor, and condition is that these materials do not hinder sulfuration.
The example of filler comprises mineral filler such as booster stage carbon black, silicon-dioxide, lime carbonate, talcum and clay and organic filler such as high styrene resin, cumarone indene resin, resol, xylogen, improved melamine resin and petroleum resin.
The example of lubricant comprises that the petroleum type lubricant is as oil, solid and whiteruss, coal tar type of lubricant such as coal tar and coal-tar pitch, wax such as beeswax, carnauba wax and lanolin and synthesized polymer material such as petroleum resin.
The example of softening agent comprises hydrocarbon ils, as paraffin, and aromatics and naphthenic oil, phthalic ester, adipic acid ester, sebate and similar softening agent.
The example of tackifier is petroleum resin, cumarone indene resin, terpene phenol resin and dimethylbenzene/formaldehyde resin.
The example of tinting material is inorganic and pigment dyestuff.
The example of whipping agent is sodium bicarbonate, volatile salt, N, N '-dinitropentamethylenetetramine, azoformamide, Diisopropyl azodicarboxylate, benzol sulfohydrazide, toluene sulfonyl hydrazide, p-toluenesulfonyl trinitride, urea etc.
Can use solvent blend or any suitable melt-mixing equipment such as Banbury mixer (Braebender Plasticorder), Banbury mixing machine, forcing machine, the mixing machine of milling, kneader or similar mixing equipment to prepare vulcanisable compound.Blending temperature in these melt-mixing equipment and time can be respectively 100 ℃-200 ℃ and 1-15 minute.Sometimes make polymeric constituent bear high-shear or extended hybrid and contain the closely even blend of phase size less than 5 microns disperse phase with formation.Some embodiments prepare the phase size less than 2 microns.
Embodiment
Following examples explanation the present invention.
Use the synthetic segmented copolymer that is used for embodiment 1 and 2 of aluminium base initiator by Living Cationic Vinyl Polymerization.The numerical value of this triblock copolymer weight % (wt%) end block and number-average molecular weight shows below:
???? Name ?? Wt% holds block ???? M n x10 -3
12tbS-80iB-12tbS ????23％tbS ????12-80-12
Wherein tbS is that t-butyl styrene and iB are iso-butylenes.As an example, being used for isobutylene-based polymers of the present invention is to be abbreviated as PIMS poly-(iso-butylene-be total to-the 4-vinyl toluene).This multipolymer comprises 96.25mol% iso-butylene and 3.75mol%PMS.GPC M nAnd M wBe respectively 173,000 and 479,000.Use two kinds of diene polymers.Budene  1207 (Goodyear Tire and Rubber Company, Akron OH) be to comprise about 98% cis-1, the polyhutadiene of 4 content, with Natsyn  22001207 (Goodyear Tire and Rubber Company, Akron OH) is the polyisoprene that comprises 92% (minimum) cis-1,4 content.By mixing in toluene, extensive drying prepares four kinds of blends in vacuum drying oven subsequently:
Embodiment 1 and 2 (Ex.1 and Ex.2) in the table 1 (numeral weight part) is that the blend and the reference examples 1 and 2 (Cont.1 and Cont.2) that comprise the segmented copolymer compatilizer do not comprise.
Table 1
Embodiment 1 Embodiment 2 Reference examples 1 Reference examples 2
?PIMS ????7.27 ????7.27 ????8 ????8
?Budene1207 ????7.27 ????- ????8 ????-
?Natsyn2200 ????- ????7.27 ????- ????8
?tbS-iB-tbS ????1.45 ????1.45 ????- ????-
?Irganox1010 ????0.16 ????0.16 ????0.16 ????0.16
Breaking strain, % ????2700 ????3500 ????1400 ????2800
Near the maximum stress of fracture, psi ????18 ????10 ????10 ????7
Wherein Irganox 1010 is stablizer (Ciba Geigy).
Use little dumb bell sample at 25 ℃ probe temperature and 2 "/these four kinds of blends are carried out tensile stress-strain-gauging under the Instron pinblock speed (ASTM D-1708) of min.As shown in Figure 1, the tbS-iB-tbS introducing in PIMS/Budene  1207 and PIMS/Natsyn  2200 blends having increased breaking strain and near the maximum stress of breaking point.Also use 1Hz frequency and 2 ℃/min heating rate that these four kinds of blends are carried out dynamic hot mechanical measurement to determine how tbS-iB-tbS influences phase behavior.These are measured those skilled in the art is known and common uses.Fig. 2 and 3 shows respectively for PIMS/Budene  1207 blends and the PIMS/Natsyn  2200 blends loss tangent (δ) as temperature function.Segmented copolymer is formed on the diffuse interface between PIMS and the diene polymer, as by in two the peak-to-peak increase loss tangent of loss tangent values (Fig. 2) or represented by narrow down (Fig. 3) at loss tangent peak.
Has the other blend of forming shown in the table 2 (numeral weight part) by melt blended preparation.Prepare several PIMS/Budene  1207 and PIMS/Natsyn  2200 with and not with 25/75 blend by weight of 12TBS-80iB-12TBS.In the Braebender mixing machine, under the spinner velocity of 180 ℃ temperature and 60rpm, carry out this blend 10 minutes.Is 0.08 180 ℃ of lower compression moldings 30 minutes with preparation thickness with every kind in the table 2 composition " pad.These molding pads are carried out tensile stress-strain-gauging (storing 24 hours) under envrionment conditions before test.Use little dumb bell sample (25 ℃ of probe temperatures, Instron pinblock speed 2 "/min, use ASTM D-1708).
Also change by the blend morphology of atomic force microscope (AFM) measurement Research owing to segmented copolymer.AFM analyzes all samples to prevent that sample is loose in low temperature facing (cryofacing) 8 hours afterwards.During the low temperature facing, sample is cooled to-150 ℃ and adopt diamond tool in cryotome, to cut.Be then under the drying nitrogen that flows, they to be warming to envrionment temperature to avoid the atmospheric water condensation in the dry device.At last, the sample of facing is installed in is used for the miniature steel that AFM analyzes and rolls pincers.Using rectangle, Si cantilever to carry out AFM in air measures.With the visual mutually size and dimension of processing and measuring with the calculating disperse phase of the AFM of all samples.
As shown in table 2, with respect to reference composition 3, introduce in PIMS/Budene  1207 blends that tbS-iB-tbS polymkeric substance (Ex.3) has increased breaking strain and near the maximum stress of breaking point.With respect to reference composition 4, introducing tbS-iB-tbS polymkeric substance (Ex.4) in PIMS/Natsyn  2200 blends has increased breaking strain.
Table 2
Reference examples 3 Reference examples 4 Embodiment 3 Embodiment 4
?PIMS ????4 ????4 ????3.64 ????3.64
?Budene?1207 ????12 ????- ????10.91 ????-
?Natsyn?2200 ????- ????12 ????- ????10.91
?tbS-iB-tbS ????- ????- ????1.45 ????1.45
?Irganox?1010 ????0.16 ????0.16 ????0.16 ????0.16
Breaking strain, % ????395 ????510 ????560 ????640
Near the maximum stress of fracture, psi ????30 ????2 ????64 ????2
?D n，μm ????1.53 ????0.57 ????0.83 ????0.25
?D w，μm ????2.17 ????0.91 ????1.24 ????0.32
?D a，μm ????2.70 ????1.15 ????1.59 ????0.40
?D v，μm ????3.03 ????1.28 ????1.86 ????0.46
?F ????0.80 ????0.82 ????0.74 ????0.71
D n=equivalent number average diameter
D w=equivalent weight-average diameter
D a=equivalent aera mean diameter
D v=equivalent volume mean diameter
F=form factor=4 π (area)/(girth) 2, the measuring of surface irregularity, littler F represents higher surface imperfection degree.
(Inc.), PIMS trace phase character is various mean diameters, D for Photoshop  5.0, AdobeSystems to use AFM measurement and image analysis n, D w, D aAnd D vAccording to table 2 data, in the size that reduces PIMS trace phase, tbS-iB-tbS is obvious to the compatible effect of PIMS/Budene  1207 and PIMS/Natsyn  2200 blends.Equally, in the presence of tbS-iB-tbS, the PIMS phase size in PIMS/Natsyn  2200 blends reduces than more in PIMS/Budene  1207 blends.This is consistent with following observation situation: the tbS homopolymer is more compatible with polyhutadiene with the polyisoprene ratio.The observation form factor that reduces in comprising two kinds of blends of tbS-iB-tbS reflects the more non-sphere and the PIMS territory of high surface area more.This long-pending increase of the field surface of per unit volume shows because the existence of tbS-iB-tbS compatilizer, is used to hinder the spatial stability of the reduction of PIMS phase coalescence and/or interfacial tension in these blends.

Claims (37)

1. compatible polymers blend comprises:
A) be selected from following isobutene polymer: polyisobutene, contain 10wt% isoprene at the most the iso-butylene random copolymers, contain 10wt% isoprene at the most the halogenated isobutylene random copolymers, contain 20wt% at the most to the iso-butylene random copolymers of ring-alkylated styrenes, contain at the most 20wt% to the halogenated isobutylene random copolymers of ring-alkylated styrenes and their mixture;
B) the unsaturated diene polymer of at least a olefinic; With
C) be used for component (a) and compatilizer (b), this compatilizer comprises that at least one repeats the polyisobutene segment and at least one comprises C 4-C 6Block-the graft copolymer of the repeating segment of cyclosubstituted vinylbenzene of alkyl or cyclosubstituted αJia Jibenyixi.
2. the composition of claim 1, wherein compatilizer comprises iso-butylene and to the multipolymer of t-butyl styrene.
3. the composition of claim 2, wherein compatilizer comprises that the GPC number-average molecular weight is 10,000-500,000 and comprise at least 10wt% to tbS-iB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or the tbS-iB-tbS or the iB-tbS-iB triblock copolymer of t-butyl styrene.
4. the composition of claim 1, wherein component (a) and (b) exist with the every 5-95 weight part of 95-5 weight part (a) (b).
5. the composition of claim 4, wherein compatilizer exists with 2-20wt% in composition, based on the blend polymer content.
6. the composition of claim 3, wherein compatilizer is that the GPC number-average molecular weight is 50,000-200,000 tbS-iB diblock or tbS-iB-tbS triblock copolymer.
7. the composition of claim 1, wherein isobutene polymer (a) comprises the multipolymer of iso-butylene and p-methylstyrene.
8. the composition of claim 7, wherein isobutene polymer (a) is to comprise the iso-butylene of benzyl chloride or bromotoluene and the halogenated copolymers of p-methylstyrene.
9. the composition of claim 1, wherein the unsaturated diene polymer of olefinic is selected from following elastomerics: the elastomer copolymer of polyhutadiene, synthetic polyisoprenes, natural rubber, divinyl and vinylbenzene or vinyl cyanide, sovprene or their mixture.
10. a blend polymer wherein vulcanizes (vulcanized), sulfuration (cured), or the composition of crosslinked claim 1-9.
11. a compatible polymers blend comprises:
A) be selected from following isobutene polymer: polyisobutene, contain 10wt% isoprene at the most the iso-butylene random copolymers, contain 10wt% isoprene at the most the halogenated isobutylene random copolymers, contain 20wt% p-methylstyrene at the most the iso-butylene random copolymers, contain the halogenated isobutylene random copolymers of 20wt% p-methylstyrene and their mixture at the most;
B) be selected from the following unsaturated diene polymer of at least a olefinic: the elastomer copolymer of polyhutadiene, synthetic polyisoprenes, natural rubber, divinyl and vinylbenzene or vinyl cyanide, sovprene or their mixture; With
C) be used for component (a) and compatilizer (b), this compatilizer comprises that at least one repetition polyisobutene segment and at least one comprise the block-graft copolymer to the repeating segment of t-butyl styrene.
12. the composition of claim 11, wherein compatilizer comprises that the GPC number-average molecular weight is 10,000-500,000 and comprise at least 10wt% to tbS-iB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or the tbS-iB-tbS or the iB-tbS-iB triblock copolymer of t-butyl styrene.
13. the composition of claim 11, wherein component (a) and (b) exist with the every 5-95 weight part of 95-5 weight part (a) (b).
14. the composition of claim 13, wherein compatilizer exists with 2-20wt%, based on the blend polymer content.
15. the composition of claim 1, wherein compatilizer is that the GPC number-average molecular weight is 50,000-200,000 tbS-iB diblock or tbS-iB-tbS triblock copolymer.
16. the composition of claim 11, wherein isobutene polymer (a) comprises the multipolymer of iso-butylene and p-methylstyrene.
17. the composition of claim 16, wherein isobutene polymer (a) is to comprise the iso-butylene of benzyl chloride or bromotoluene and the halogenated copolymers of p-methylstyrene.
18. the composition of claim 11, wherein the unsaturated diene polymer of olefinic is selected from following elastomerics: the elastomer copolymer of polyhutadiene, synthetic polyisoprenes, natural rubber, divinyl and vinylbenzene or vinyl cyanide, sovprene or their mixture.
19. a blend polymer, wherein sulfuration (vulcanized), sulfuration (cured), or the composition of crosslinked claim 11-18.
20. a compatible polymers blend comprises:
A) be selected from following isobutene polymer: polyisobutene, contain 10wt% isoprene at the most the iso-butylene random copolymers, contain 10wt% isoprene at the most the halogenated isobutylene random copolymers, contain 20wt% at the most to the iso-butylene random copolymers of ring-alkylated styrenes, contain at the most 20wt% to the halogenated isobutylene random copolymers of ring-alkylated styrenes and their mixture;
B) the unsaturated diene polymer of at least a olefinic; With
C) comprise iso-butylene and to the compatilizer of t-butyl styrene multipolymer, wherein this compatilizer comprises that the GPC number-average molecular weight is 10,000-500,000 and comprise at least 10wt% to tbS-iB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or the tbS-iB-tbS or the iB-tbS-iB triblock copolymer of t-butyl styrene.
21. the composition of claim 20, wherein component (a) and (b) exist with the every 5-95 weight part of 95-5 weight part (a) (b).
22. the composition of claim 21, wherein compatilizer exists with 2-20wt%, based on the blend polymer content.
23. the composition of claim 20, wherein compatilizer is that the GPC number-average molecular weight is 50,000-200,000 tbS-iB diblock or tbS-iB-tbS triblock copolymer.
24. the composition of claim 20, wherein isobutene polymer (a) comprises the multipolymer of iso-butylene and p-methylstyrene.
25. the composition of claim 24, wherein isobutene polymer (a) is to comprise the iso-butylene of benzyl chloride or bromotoluene and the halogenated copolymers of p-methylstyrene.
26. the composition of claim 20, wherein the unsaturated diene polymer of olefinic is selected from following elastomerics: the elastomer copolymer of polyhutadiene, synthetic polyisoprenes, natural rubber, divinyl and vinylbenzene or vinyl cyanide, sovprene or their mixture.
27. a blend polymer, wherein sulfuration (vulcanized), sulfuration (cured), or the composition of crosslinked claim 20-26.
28. one kind by forming the method for compatible polymers blend in conjunction with following material:
A) be selected from following isobutene polymer: polyisobutene, contain 10wt% isoprene at the most the iso-butylene random copolymers, contain 10wt% isoprene at the most the halogenated isobutylene random copolymers, contain 20wt% at the most to the iso-butylene random copolymers of ring-alkylated styrenes, contain at the most 20wt% to the halogenated isobutylene random copolymers of ring-alkylated styrenes and their mixture;
B) the unsaturated diene polymer of at least a olefinic; With
C) be used for component (a) and compatilizer (b), this compatilizer comprises that at least one repeats the polyisobutene segment and at least one comprises C 4-C 6Block-the graft copolymer of the repeating segment of cyclosubstituted vinylbenzene of alkyl or cyclosubstituted αJia Jibenyixi.
29. the method for claim 28, wherein compatilizer comprises iso-butylene and to the multipolymer of t-butyl styrene.
30. the method for claim 29, wherein compatilizer comprises that the GPC number-average molecular weight is 10,000-500,000 and comprise at least 10wt% to tbS-iB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or the tbS-iB-tbS or the iB-tbS-iB triblock copolymer of t-butyl styrene.
31. the method for claim 20, wherein component (a) and (b) exist down with the every 5-95 weight part of 95-5 weight part (a) (b).
32. the method for claim 31, wherein compatilizer exists with 2-20wt%, based on the blend polymer content.
33. the method for claim 32, wherein compatilizer is that the GPC number-average molecular weight is 50,000-200,000 tbS-iB diblock or tbS-iB-tbS triblock copolymer.
34. the method for claim 28, wherein isobutene polymer (a) comprises the multipolymer of iso-butylene and p-methylstyrene.
35. the method for claim 34, wherein isobutene polymer (a) is to comprise the iso-butylene of benzyl chloride or bromotoluene and the halogenated copolymers of p-methylstyrene.
36. the method for claim 28, wherein the unsaturated diene polymer of olefinic is selected from following elastomerics: the elastomer copolymer of polyhutadiene, synthetic polyisoprenes, natural rubber, divinyl and vinylbenzene or vinyl cyanide, sovprene or their mixture.
37. the method for claim 28-36 further comprises sulfuration (vulcanizing), and is crosslinked, or sulfuration (curing) step.
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